Process of alkylating hydrocarbons



April 28, 1942.

D. H. Pufr'NEY PROCESS OF ALKYLATING HYDROCARBON'S 2 Sheets-Sh April 28, 1942 I D. H. PUTNEY 2,281,248

PROCESS 0F ALKYLATING HYDROCARBONS Filed Aug. 2, 1941 2 sheets-snee@ 2 Paten-ted Apr. 28, 1942 UNITED STATES PATENT OFFICE PROCESS F ALKYLATING HYDROCARBONS David H. Putney, Kansas City, Mo., assignor to Stratford Development Corporation, Kansas City, Mo., a corporationv of Delaware y application August 2, 1941, seria1No.4o5,199

(o1. 19e-1o) 5 Claims.

charging to the alkylation reaction zone.

lso-parainic hydrocarbons, such as isobutane, iso-pentane and the like have been alkylated with olefinic hydrocarbons in the presvence of catalysts such as sulfuric acid and phosphoric acid. Iso-butane has been reacted with butylene to produce iso-octane. The reaction takes place in the presence of a condensation catalyst and is exothermic.

Throughout this specification, the term alkylate is used to indicate a fraction of the vtotal condensation product which is suited for blend ing to produce premium aviation or motor fuel, and the term total alkylate constitutes all condensation products removed from the alkylation stage. Acid-olefin ratio, as used herein, means the volumetric relationship which the acid catalyst bears to the absorbed olefin. Time factor as used herein, is the residence time that the olen remains in the acid catalyst from the time 'of absorption to its introduction into the alkylation stage. y

In an alkylation system such as described in application Serial No. 376,584, filed January 30, 1941, wherein the olefinic hydrocarbons are rst absorbed in the recycled acid settled from the eluent from the alkylation stage prior to recharging the mixture of acid catalyst and olenic hydrocarbons to the alkylation contactor, it has been discovered that a definite relationship exists between the quality of the alkylate produced, the acid-olefin ratio and the residence time of the olefin in the acid before reaching the alkylation reaction zone.

It is believed that investigators have failed to achieve good results when charging olens absorbed in acid to alkylation plants for the reason that they have failed to realize the importance of the relation which exists' between acid-olen ratio and the residence time factor of the olen in the acid as controlling operating variables.

An advantage of the present method is the absorption of the olenic hydrocarbons in the catalyst, thereby making possible the elimination 'of diluent and inert materials from the charge, suc as normal butane.`

A further advantage of the process lies in the Another advantage of the process is its ability to utilize for absorbing the olefin, acid recycled directly from the alkylation zone Without dilution or fortification.

Still another advantage of the process is the production of a better'quality total alkylate as Y compared to other methods utilizing preliminary olefin absorption in the catalyst.

In the accompanying drawings which form part of the instant specification and are to be read in conjunction therewith, and in which like reference numerals are used to indicate like parts in the Various Views; i

Fig. 1 is a now diagram of the process, showing the apparatus in diagrammatic form.

Fig. 2 is a chart in which there has been plotted octane number against the acid-olen ratio divided by the time factor.

Fig. 3 is a chart showing alkylateyield (280 F. end point) in per cent of total alkylate plotted against the acid-olefin ratio, divided by the time Fig. 4 is a modified type of absorber-separator.

Referring to the drawings; at l is shown a contactor, the structural details of which are disclosed in a prior application, filed in the name of David H. Putney, Serial No. 370,609, on December 18, 1940.' Numerals 2, 3, and 4 designate settlers; numerals 5, 6, l, 8, 9, I0, ll, l2, I3, 64, and 103, pumps.

That portion of the apparatus comprising the absorption step includes a Chiller I4, a mixer I5, and a separator I6.

The refrigeration system used for extracting heat and for pre-cooling the catalyst prior-to absorption of the olefin comprises a compressor Il, a condenser I8 and a receiver I9. A separator 20, located above the contactor l serves as a collecting reservoir .for the -refrigerant prior to its Y introduction to the heat exchanger, positioned in the top of the contactor, and permits separation of the gaseous material from the liquid refrigerant which is discharged from the heat exchanger. Fractionation equipment for removing unreacted iso-paraiiins from the alkylate, equipment for` stabilizing and rerunning the alkylate include the alkylate stabilizer 2| and rerun tower 22.

Equipment for separating small amounts of a1- kylate and polymerized olens which may be carried with the iso-butane and normal butane recovered from the absorption system include a fractionator 23 and a de-isobutanizer 24.

Describing the operation, the feed stock preferably includes unsaturated hydrocarbons which comprise normally gaseous materials resulting fromv the cracking of hydrocarbons or hydrocarbon gases, the destructive hydrogenation of hydrocarbons or dehydrogenation of hydrocarbons and iso-paraflins having a boiling range below gasoline, for example, isobutane or iso-pentane.

Such feed stocks normally contain appreciable quantities of parailins such as normal butane.

'Ihe method shown contemplates the use of a feed stock which has already been denuded of hydrocarbons having less than 4 carbon atoms.`

Such preliminary treatment is conventional in the art of alkylating C4 hydrocarbons. The olefin hydrocarbons and iso-parainic hydrocarbons are charged from any convenient source through pipe 25 and are passed through the heat exchanger 26 where they are broughtdn heat exchange relationship with cooler hydrocarbons introduced to the heat exchanger through line 21 and discharged therefrom through line 28.

After` being cooled in the heat exchanger, the feed stock passes through pipe 29 and is introduced into the mixer I5 where it is intimately combined with the recycled catalyst charged to the mixer through pipe 30. rIfhe mixture of olefin absorbed in the catalyst passes from the mixer I5 through pipe 3| into the separator I6. The separator is so designed that it is operated full of liquid and the time of separation is reduced to a minimum. In place of the mixing and separating apparatus shown, this equipment may be replaced either by conventional centrifuges for effecting rapid separation of the two liquids or by a modied type of combined absorber-mixer and separator shown in Fig. 4. When this modified absorber-mixer is used, instead of absorbing the olen hydrocarbons in the liquid phase, they are vaporized with the feed stock and absorbed into the catalyst from the vapor mixture. The unabsorbed hydrocarbons pass from the absorber as vapor and must be reduced to liquid form in conventional apparatus, not shown.

Referring to Fig. 4, the absorber-mixer consists of a shell 32, which has a tapered bottom and is flanged at 33 to receive the flange 34 of a motor and pump assembly 35. 'I'he motor shaft is extended into the body of the shell 32, as shown at 36 and, on the upper end of the shaft is mounted a rotating shrouded disk 31. Surrounding the shaft is an open-ended tube 38 in the lower part of which are apertures'or inlet openings 39. Into the top of the shell is a pipe connection 40, which terminates just above the shrouded disk 31. In the upper part of the shell is a baille plate 4I having a center aperture 42 which directs the vapors rising through the shell toward the center and through an annular opening around the pipe 40. In the upper part of the motor pump assembly is a centrifugal pump rotor 43, mounted upon the shaft 36 and rotating with the shaft at the same speed as the shrouded disk.

As previously suggested, this absorber-mixer ,takes the place in the system of the mixer I5 and the separator I6. The hydrocarbon feed charged through line 29 is introduced into the shell of the absorber-mixer in vapor form through nozzle 44, the end of which extendsl centrally into the shell of the mixer. The chilled acid from chiller I4 passing through line 30, is introduced through pipe 40 into the top of the mixer and is distributed by the rotating disk 31 in a thin film horizontally from theperiphery or outer edge of the disk. 'Ihe hydrocarbon vapor introduced through pipe 44 rises through the shell and, in passing through this thin film or atomized screen of acid, has the olefin portion thereof absorbed Ain the acid. The; remainder of the hydrocarbon or unabsorbed vapor passes upward throughthe aperture 42 and is discharged from the shell ofthe mixer through pipe 45. On discharge from the mixer, the hydrocarbon vapors are reduced to liquid form in conventional compression condensing apparatus, well known in the art, and thereafter is passed into the fractionator 23 to be treated in the same manner as the liquid hydrocarbons discharged through line 28.

The acid catalyst projected from the disk which' absorbs the olenic hydrocarbons, gravitates to the bottom of the mixer and is picked up by pump 43, and discharged through pipe connection 46 to contacter I.

Returning now to the operation Where the mixer and separator are used, as shown in Fig. 1, the acid and olefin mixture being of higher specific gravity than the hydrocarbons, settles to the bottom of the separator. I6 and is drawn off through pipe 41 and is charged by pump 5 through line 46 to contactor I. The unabsorbed hydrocarbons, including iso-butane and normal butane, pass off from the top of the separator through line 48 to settler 4. In this settler, acidity in the hydrocarbons is removed by a soda mixture circulated through the settler by means of pump I0 and connecting pipes 49 and 5I).` Through pipe 5I fresh soda may be supplied and spent soda removed through pipe 52. Suitable valves are supplied in these pipes to control the introduction or withdrawal of the soda from the cycle. The hydrocarbons, after soda treatment, are removed from the top of the settler through pipe 21, brought in heat exchange relation with the feed stock, and then discharged through pipe 28 to the fractionator 23.

'I'he temperature of the fractionator is maintained by a heating coil 53 in the bottom of the tower and a redux system at the top includes a pump I3, a condenser 54, a receiver 55, an overhead pipe from the tower 56 and a return pipe 51, the system being conventional in the art. From the bottom of the fractionator through pipe 58 are removed liquids heavier than C4 fractions. From the refluxing system in liquid form are removed iso-butane and normal butane fractions through the pipe 59. These hydrocarbons are directed to the de-isobutanizer 24. The temperature in the de-isobutanizer is controlled in a similar manner by a heating coil 60 and a top tower reuxing system including a drawoil' pipe 6I, a condenser 62, a receiver 63, pump 64, and return line 65. From this refiuxing system is removed iso-butane through .line 66, which iso-butane is accumulated in the feed tank 61. From the bottom of the de-isobutanizer we remove normal butane through pipe 68, which is discarded from the system.

In the event the product withdrawn from the fractionator through line. 58 shows appreciable quantities of olefins or unalkylated hydrocarbons, a line 69 connected between the feed tank 61 and pipe 58 furnishes a means for diverting such materials to the feed tank. I-f this material contains considerable alkylated hydrocarbons they .are passed directly to the alkylate rerun tower 22 through pipe 10, pump 9, and line 1I.

Returning to the materials charged to the alkylate reaction stage, the Acatalyst containing the absorbed olefin is supplied through pipe 46. The iso-paraflins accumulated in the tank 61 are charged through pipe 12, pump'l and pipe 13, and are introduced to the `contactar I where they are brought in rapid and intimate contact with the catalyst-olefin mixture. Rapidity of circulation of the contents of the contactor is an important adjunct to a proper reaction.

Alkylation proceeds with the generation of exothermicheatwhich is dissipated by a. refrigerating medium, circulated through a heat exchanger, the top of which is designated by the numeral 14 and which extends down into the mixing portion of the contactor. The contactor is so constructed that, during alkylation, the reactants are rapidly circulated through the heat exchanger. f

A closed ammonia system is used for removing this exothermic heat and chilling'the catalyst prior to the absorption of the olen. Ammonia is supplied through pipe 15 to the receiverv I9. Gaseous ammonia is compressed in compressor |1 and is discharged through pipe 16 through condenser 8, thence to' the receiver I9 through pipe 11. The cool liquid product from the receiver is distributed through pipes 18 and 19 to the catalyst-Chiller I6. A return line 80 from the chiller directs the ammonia vapors for recompression, to the suction side of the compressor |1. The ammonia refrigerant is also supplied from the receiver 9 through pipes 18 and 8| to separator 20, from whichv the liquid product is supplied through line 82 to heat exchanger 14. Ammonia vapor and entrained liquid is returned from the exchanger 14 through pipe 83, back to the separator 20. The separated vapor is taken oi from the top of the separator and is returned through pipe 84 to the compressor.

Desired temperatures in the catalyst-chiller I0 and temperatures of reaction in the alkylation stage are controlled by manipulation of the valves in lines and 8d, which regulate the pressure of the ammonia refrigerant.

The hydrocarbon catalyst mixture discharged from the contactor E passes through pipe 85 to separator 2 where the catalyst is separated from the alkylated hydrocarbon. The catalyst accumulated in the bottom of the settler, with or Without dilution or addition of stronger acid, is returned through pipe 86, pump 6 and line 81 to' the acid chiller Id and oleiin-absorption system, previously described. Acid of alkylating strength that is from 85% to 96% HaSO is-therefore used in the olenabsorption system. plated also to recycle a controlled amount of the alkylate withdrawn through pipe 85 directly to the absorption system by means of bypass line 85a which directs the catalyst hydrocarbon mix around the settler 2.

To augment th'e acid catalyst from time to time if operating continuously, or to recharge the acid cycle in the event batch operation is used, acid is supplied through pipe 88 and spent acid withdrawn through pipe 89. Both of these z ,Iizer are taken 01T iso-parafilns containing a.

small amount of butane, through line 91, which pass through a reuxing system consisting of a It is contems condenser 98, receiver 99, pump I2, and a return line |00. From this refluxing system are removed liquid-is-parailins through pipe |0|, to be directed either to the feed tank 61 through pipe' |02 or to the de-isobutanizer through pump |03 and pipe ||2. Normally, the hydrocarbons bled from' the reuxing system connected into the top of the alkylate stabilizer, are passed to the feed tank 61. Should any normal butane be accumulated in the system, a portion of the stream withdrawn through pipe |0| is diverted to the deisobutanizer to exhaust this butane.

In the bottom of the alkylate stabilizer is a heating coil |04 formaintaining proper temperatures in the tower.

From the bottomlof the alkylate stabilizer is removed the total alkylate through pipe |05,

which is forced by pump 9 through pipe 1| the alkylate rerun tower 22.

Overhead materials are removed from the top of the rerun tower 22'through pipe |06 and the alkylate bottom taken ol from th'e lower portion of the tower through pipe |01. This tower is equipped with a refluxng system similar to those previously explained. It consists of the withdrawal line |06 connected into the top of the towar, condenser |08, receiver |09, pump and return pipe 0. The ultimate productfrom the system, dened as alkylate heretofore and which constitutes an end point alkylate, is withdrawn from the reux system of the alkylate rerun tower 22 through pipe Test runs utilizing the process explained were made under dierent operating conditions to determine the eiiect of operating variables. It was readily noted' that, in order to obtain good results, it was necessary to use large quantities of acid to that portion of the system in which the olen was absorbed by the catalyst-acid in the order of volumes of acid or more to l volume of olen. Under these conditions, itwas possible to produce a total alkylate showing a rerun yield of 96 per cent of 280 F. end point having y an octane number of 94.8 C. F. R. A. S. T. M. As the acid-olefin ratios were lowered, the quality of the product depreciated both in rerun yield and octane number. Due to limitations of apparatus, the residence time of the olen vin the acid necessarily became longer as the quantity of acid was decreased. At an acid-olen ratio of 15 or 20` to 1 the product was very poor. Afterapparatus changes were made which lenabled the use of shorter time factor, improved results were obtained even at'th'ese lower acidolefin ratios.

When attempting to correlate the accumulated data from a large number of test runs, it was discovered that a factor could be developed Y from the acid-olefin ratio and the residence time of the olen in the acid which made possible the plotting of both the octane number and the rerun yield against this factor lto make a smooth curve in each case.

This factor is obtained by taking the volume 'ratio of acid to olefin fed to the absorber and dividing the ratio thus obtained bythe totalV time in minutes that the olefin is in contact with the l acid from the initial meeting of the two constituents in the absorber or mixer until the ole- 1in-bearing acid enters the alkylation reaction zone or contactor.

In other words, the higher the acidolen ratio and/or the shorter the residence time of the absorbed olen in the acid, the better is the alkylate produced` in the matter of both rerun yield and octane. Curves showing rerun yield and octane plotted against the acid-olefin ratio, divided by the time factor, form a part of the speciication.

Tests plotted on the curve were conducted at operating temperatures of 40 to 50 F. and 22 F. maintained in the absorber and separator.

The effect of decreased temperature was to improve the results by raising the entire curve for both octane number and rerun yield. These low temperatures could be obtained only by ob-I taining relatively low temperatures of the refrigerant in the refrigeration cycle. For this reason, a closed ammonia system was adopted in place of utilizing the iso-butane recovered from the alkylate separator as a refrigerant. The invention contemplates, however, that constituents of the alkylation reaction may be used as a refrigerant in the cooling cycle, as well as ammonia.

All of the runs considered in these tests were conducted at high iso-butane olen ratios in the alkylation contactor so that any possible detrimental eiiect of low ratios in the alkylation zone were eliminated. In other words, the conditions in the alkylation contacter were optimumand could be considered as constant for all runs Assuming, therefore, that conditions of the alkylation reaction are properly established -for good results, then this acid olefin ratio time factor in the absorption section becomes the governing factor for best results at any given oper` ating temperature.

'I'he magnitude of improvement to be expected from an increase in the acid olefin ratio time `factor will be different for each operating temperature on the absorber separator system as shown in Figs. 2'and 3. A different curve can,

be developed for each temperature range but the acid olefin ratio time factor remains the controlling variable in each case.

Figs. 2 and 3 show that, unless the ratio time factor is greater than 10, a decidedly inferior alkylate will be produced. The ratio time factor should be maintained greater than 1,0 and preferably greater than 50. Excellent results are obtained even with low acid olefin ratios provided the residence time of olefin in the acid is suiiiciently short to bring the ratio time factor up to the desired figure.

'For example, assuming an acid olefin ratio of to 1 and atime factor of .3 of a minute for the residence time of the olefin in the acid, a ratio time factor of 50 is obtained. Under these conditions and with a temperature range of from 40 to 50 F. in the absorber, the curves in Figs. 2 and 3 show the rerun. yield 83 per cent, the octane 'number 90.6. Assuming the same acid olen ratio time factor and temperature of 22 F. in the absorber, these curves show a rerun yield of alkylate of 95 per cent and an octane number 94.7. Results at 22 F. show an excellent product and an improvement over those at the higher temperatures.

. Contrasting these results by increasing the time factor, assuming that the acid olefin ratio remains 15 to 1 and the time is increased from .3 of a minute to 2 minutes; the ratio time factor now becomes 'Z1/2. The rerun yield, utilizing this ratio time factor at a temperature range of from 40 to 50 F. would be 65 per cent, the octane number 88. Using the same ratio time factor4 and the octane numbe.92.5, which is a relatively inferior product.

Having thus described my invention, I claim:

1. A method of alkylation in whichiso-paraflnic hydrocarbons are alkylated with olenic hydrocarbons in the presence of a condensation catalyst in an alkylation stage and the catalyst recycled for reuse, the improvement which comprises selectively absorbing the oleiinic hydrocarbons of the charge in the catalyst prior to alkylation and limiting the residence time period of contact of the catalyst and olens in minutes to less than one tenth of the volumetric catalyst olefin hydrocarbon ratio.

2. A method of alkylation in which iso-parafflnic hydrocarbons are alkylated with olenic hydrocarbons in the presence of a condensation catalyst in an Aalkylation stage and the catalyst recycled for reuse, the improvement which comprises selectively absorbing the olenic hydrocarbons of the charge in the catalyst prior to alkylation and limiting the residence time period of contact of the catalyst and olefins in minutes to less than one tenth of the volumetric catalyst olen hydrocarbon ratio, bringing a refrigerating medium in indirect contact with the reactants in the alkylation stage and the recycled catalyst to maintain the respective materials at predetermined temperatures.

3. A method of alkylation in which iso-parafiinic hydrocarbons are alkylated with olenic hydrocarbons in the presence of a'condensation catalyst in an alkylation stage and the catalyst recycled for reuse, the improvement which comprisesselectively absorbing the olefinic hydrocarbons of the charge in the catalyst prior to alkylation and limiting the residence time `period of contact of the catalyst and olefins in minutes to less than one'tenth of the volumetric catalyst olefin hydrocarbon ratio, and maintaining the temperature of the mixture during the residence time of the olens in the catalyst below 50 F. y 4. A method of alkylation in which isoparaf nic hydrocarbons are alkylated with olefinic hydrocarbons in the presence of a condensation catalyst in an alkylation4 stage and the catalyst recycled for reuse, the improvement which comprises selectively absorbing the oleiinic hydrocarbons of the charge in the catalyst prior to alkylaftion and limiting the residence time period of contact of the catalyst and olefins in minutes to less than one tenth of the `volumetric catalyst olefin hydrocarbon ratio, separating parainic and iso-paraflinic hydrocarbons from the mixture of catalyst and charge prior to the introduction of the catalyst olefin mixture to the alkylation stage.

5. A method of alkylation in which iso-parafnic hydrocarbons are alkylated with olenic catalyst and charge prior to the introduction of the catalyst olefin mixture to the alkylation stage, and charging the iso-paraiiinic hydrocarbons to the alkylation stage.

DAVID H. PU'I'NEY. 

